Soaps and detergents containing alpha-oxy(oxo)sulfides as perfumes

ABSTRACT

Perfumed articles which are soaps or detergents containing alpha oxo sulfides having the structure: ##STR1## wherein R is methyl or hydrogen and X is a ketone having the structure: ##STR2## and Y is one of methyl, methallyl having the structure: ##STR3## 1-propyl, 2-methyl-1-propyl and acetyl which have imparted thereto sweet, green, floral, herbal, vegetative, basil-like, minty, melony, grapefruit, fruity and alliaceous aromas with yara, neroli and/or verdima-like nuances.

This application is a divisional of application for U.S. Pat. Ser. No.723,534, filed on Sept. 15, 1976 now Pat. No. 4,065,408.

BACKGROUND OF THE INVENTION

There is a continuing search for materials having desirable fragranceproperties. Such materials are sought either to replace costly naturalmaterials or to provide new fragrances or perfume types which have notheretofore been available. Especially desirable qualities for substanceshaving interesting hyacinth fragrances, or narcisse fragrances, orviolet fragrances, or oriental vetivert fragrances, or otto of rosefragrances are stability and persistence, particularly in a wide varietyof perfumed articles (e.g., soaps, detergents and powders), perfumecompositions and colognes, ease of manufacture and intensity of aroma.

Prior to this last decade it was the general opinion among those skilledin the art that compounds containing the mercapto or -SH moiety orsubstituted mercapto or -SR moiety (where R is an organic group such asalkyl or acetyl) were not desirable for use in conjunction withfragrance materials and perfumed articles such as soaps, detergents andpowders. However, within the last decade such compounds have beenascertained to be highly useful in perfumery.

Thus, for example, British Pat. Nos. 1,423,914 and 1,423,915 issued onFeb. 4, 1976, teach that certain mercapto derivatives which arealiphatic or cycloaliphatic compounds having the formula: ##STR4##wherein X¹ represents a hydroxyl group or an acyloxy group, and X²represents a hydrogen atom; R¹, R², R³ and R⁴ may be the same ordifferent and each represents a hydrogen atom or a univalent aliphatichydrocarbyl group; or R¹ and R³ or R⁴, together with the interveningcarbon atoms, constitute a cycloaliphatic ring, are useful as perfumingagents as exemplified by adding 3-methylthio-hexanol to a perfume basecomposition of the "Fleuri" type wherein the 3-methylthio-hexanol issaid to give rise to a green, fruity aroma reminiscent of that ofrhubarb.

Furthermore, for example, Canadian Pat. No. 983,050 issued on Feb. 3,1976, teaches that 3,7-dimethyl-octa-2,6-dienyl-mercaptan (thiogeraniol)of the formula: ##STR5## is used in making up a "synthetic buchu leafoil" and imparts to a lavender type composition a greener and moreherbal fragrance. USSR Pat. No. 345,677 teaches thatpara-menthane-8-thiol-3-one is useful as a synthetic black currentflavoring for foodstuffs. This compound has the structure: ##STR6##German Offenlegungschrift Pat. No. 2,316,456, published on Oct. 11, 1973discloses the use of certain thiol alcohols or their correspondingesters in perfumery and in perfumed articles, such as detergents,cosmetics and waxes. Such mercapto alcohols having the genericstructure: ##STR7## wherein R₁ is a hydrocarbon moiety having from 1 upto 7 carbon atoms and R₂ is one of hydrogen, methyl or ethyl.

U.S. Pat. Nos. 3,950,429 issued on Apr. 13, 1976, and 3,952,062 issuedon Apr. 20, 1976, disclose certain alkylthiosubstituted oxo-terpenoidshaving 10 carbon atoms in the terpenoid skeleton as useful in perfumeryand in flavors, particularly for providing vegetable notes. The genericstructure of the compounds is as follows: ##STR8## wherein R¹ representshydrogen or together with R⁴ represents a C -- C bond,

R² represents hydrogen or together with R⁶ represents adimethylmethylene group, or, when R⁶ is isopropyl, together with R⁵represents a C C bond,

R³ represents hydrogen or together with R⁶ represents adimethylmethylene group,

R⁴ represents hydrogen or together with R¹ represents a C C bond,

R⁵ represents hydrogen or, when R⁶ signifies isopropyl, together with R²represents a C C bond,

R⁶ represents isopropyl or together with R² or with R³ represents adimethylmethylene group,

R⁷ represents methyl,

X represents a C C double bond taking the place of a C C single bond,

m = 0 to 2,

Y represents oxo bound to a primary or secondary C-atom and Z representsmercapto or lower alkylthio located in the β-position to the carbonylfunction,

provided that when R², R³ and R⁵ represent hydrogen, R⁶ representsisopropyl, R⁴ together with R¹ represents a C C bond, Y is β to thecarbon atom bearing the substituent R⁷, m= o, Z is α to the carbon atombearing the substituent R⁵ and β to the carbon atom bearing thesubstituent R³, then Z represents alkylthio.

However, none of the disclosure of the prior art contains a teaching tothe effect that compounds having the generic structure: ##STR9## whereinR is one of methyl or hydrogen; X is one of ##STR10## and Y is one ofmethyl, methallyl having the structure: ##STR11## n-propyl,2-methyl-1-propyl or acetyl, has the ability to create an intense sweetand/or green and/or floral and/or herbal and/or vegetative and/orbasil-like and/or minty and/or melony and/or grapefruit and/or fruityand/or alliaceous aroma with yara and/or neroli and/or verdima nuancesas is carried out using the instant invention. Furthermore, othersubstituted mercaptans in the prior art which are shown to be useful inperfumery and other mercaptans in the prior art which are shown to beuseful in perfumery are indicated to have rhubarb-like or berry or othertype floral fragrances, e.g., ionone and irone derivatives having thestructure: ##STR12## as disclosed in British Pat. No. 1,327,320,published on Aug. 22, 1973, wherein one of the dashed lines represents adouble bond, and where R is hydrogen or alkyl.

Certain α-oxomercaptoalkanes are disclosed in the prior art, but theiruses in perfumery, in perfumed articles or in colognes are notdisclosed. Thus, U.S. Pat. No. 3,773,524, issued on Nov. 20, 1973,discloses the use of α-ketothiols of the formula: ##STR13## wherein R₁is methyl or ethyl; and R₂ and R₃ are hydrogen, methyl or ethyl to alterthe meat flavor and aroma of foodstuffs. U.S. Pat. No. 3,892,878, issuedon July 1, 1975, discloses the use of certain α-hydroxymercaptoalkanesto alter the flavor of foodstuffs, for example, 2-mercapto-3-butanolused in meat flavors. The genus disclosed by U.S. Pat. No. 3,892,878 isas follows: ##STR14## wherein X is oxygen or sulfur, n is 0 or 1, R₁ -R₇are the same or different and each is hydrogen or lower alkyl of 1-4carbon atoms, a and b are the same or different and each represents aninteger of from 0 to 10 when n is 0 and when n is 1, a and b are thesame or different and each represents an integer of from 1 to10.3-mercaptoheptanone-4 is disclosed per se in U.S. Pat. No. 2,888,487,issued on May 26, 1959. 3-mercapto-2,6-dimethyl-heptan-4-one isdisclosed in Chem. Abstracts 6478 (d) Vol. 62, 1965 (abstract ofAsinger, Diem and Schaefer, Monatsh. Chem. 95 (4-5), 1335-54 (1964).Beilstein E-IV-1 discloses 2-mercapto-2,4-dimethyl-pentan-3-on page4039, 1-mercapto-octan-2-on at page 4040; and 1-mercapto-nonan- 2-on at4052 and 1-mercapto-undecan-2-one at page 4060.

U.S. Pat. No. 3,922,366 issued on Nov. 25, 1975, discloses theenhancement of foodstuffs by addition of a small but effective flavormodifying amount of a compound of the general formula: ##STR15## whereinR₁ is hydrogen or alkyl and R₂ is alkyl or furfuryl. The flavor nuanceswhich are enhanced or altered are those which are found in coffeeflavors and aromas.

THE INVENTION

The invention comprises novel compositions, perfumed articles andcolognes containing α-oxy(oxo) sulfides having the structure: ##STR16##wherein X is one of: ##STR17## R is one of methyl or hydrogen and Y isone of methyl, methallyl having the structure: ##STR18## acetyl,1-propyl or 2-methyl-1-propyl and processes for manufacturing suchcompositions, perfumed articles and colognes, the specific embodimentsof which are described hereinafter by way of example and in accordancewith which it is now preferred to practice the invention.

Briefly, the present invention provides the α-oxy(oxo) sulfides havingthe structure: ##STR19## in perfume and fragrance modifying, augmentingor enhancing materials and perfumed articles including soaps, detergentsand powders as well as colognes.

Such α-oxy (oxo) sulfides are obtained by reacting an alkanone with SO₂Cl₂ to form an α-chloroalkanone; reacting the α-chloroalkanone with analkali metal mercpatide to form an α -substituted mercaptoalkanone whichcan be used for its perfumery properties; or, if desired, reacting theα-substituted mercaptoalkanone with a reducing agent such as an alkalimetal borohydride in order to obtain an α-hydroxy-substitutedmercaptoalkane. Thus, the aforementined reaction sequence is illustratedas follows: ##STR20## wherein Y is one of methallyl having thestructure: ##STR21## methyl, 1-propyl, 2-methyl-1-propyl or acetyl; andR is one of methyl or hydrogen.

The reaction between the SO₂ Cl₂ and the ketone preferably takes placein the absence of a solvent at a temperature of between 15° C and 40° C.The SO₂ Cl₂ is preferably added to the ketone. At the end of thereaction the reaction mass is worked up, the chlorinated ketone beingdistilled in vacuo.

The resulting chlorinated ketone is reacted with an alkali metalmercaptide, preferably a sodium mercaptide, preferably which ispre-prepared by reaction of sodium methylate with the appropriatemercaptan in methanol. The chlorinated ketone is preferably contained inan inert solvent, e.g., in a methanolic solution. Preferably themethanolic solution of chlorinated ketone is slowly added to thepre-prepared alkali metal mercaptide at a temperature of between 0° Cand 30° C; preferably between 15° C and 30° C. The reaction mass is thenextracted with a solvent such as methylene chloride, and the resultingextract is then worked up using evaporation and distillation techniqueswhereupon the α-substituted mercaptoalkanone is recovered. The resultingα-substituted mercaptoalkanone is then used "as is" for its perfumeryproperties; or it may be further reacted with a reducing agent such asan alkali metal borohydride, conveniently sodium borohydride. Thereaction with sodium borohydride takes place in an inert solvent such asanhydrous ethanol at a temperature of between 20° C and 35° C. Asolution in anhydrous ethanol of the α-substituted mercapto-alkanone isadded to a solution in anhydrous ethanol of the alkali metalborohydride. The reaction is carried out over a period of time betweentwo and ten hours. At the end of the reaction the reaction mass isconcentrated and is then admixed with water. The resulting mixture isthen acidified to a pH of between 2 and 3 and then extracted with aninert extraction solvent such as methylene chloride. The methylenechloride extract is then dried, evaporated and the resultingα-substituted mercapto-alkanol is distilled in vacuo or isolated by GLCtrapping.

Alternatively, the α-chloroketone may be reacted with an alkali metalhydrosulfide such as sodium hydrosulfide, NaHS, to form thecorresponding α-mercaptoketone. The α-mercaptoketone may then be reactedwith base (e.g., sodium methoxide) to form the alkali metal salt. Thealkali metal salt of the α-mercaptoketone is then reacted with an alkylor alkenyl halide (e.g., methallyl chloride) thereby forming the desiredα-substituted mercaptoketoalkane which may then if desired be used assuch for its organoleptic properties, or it can be reduced with thealkali metal borohydride to the corresponding α-substitutedmercaptohydroxyalkane. This reaction sequence is illustrated as follows:##STR22## wherein R and Y are as defined above.

Specific examples of α-oxy(oxo) sulfides produced using theafore-mentioned process and their perfumery properties are as follows(as set forth in Table I, below):

                                      TABLE I                                     __________________________________________________________________________    COMPOUND   STRUCTURE        AROMA                                             __________________________________________________________________________    3-methylthio-4-  heptanol                                                                 ##STR23##       At 1% in food grade ethanol, a sweet, green,                                  floral, herbal, vegetative note.                  3-methylthio-4-  heptanone                                                                ##STR24##       At 1% in food grade ethanol a green, minty,                                   herbaceous note with vegetative basil notes       3-propylthio-4-  heptanol                                                                 ##STR25##       Fatty, cucumber, onion (scallion, shallot)                                    aroma with some green melon and floral                                        nuances.                                          3-thioacetyl-2,6-  dimethyl-4- heptanone                                                  ##STR26##       At 1% in food grade ethanol, a sweet, meaty,                                  vegetable aroma with somewhat of a grape-                                     fruit topnote.                                    3-isobutylthio-4-  heptanone                                                              ##STR27##       Evaluated at 1% in food grade ethanol, a                                      meaty, onion aroma with a green, spicey and                                   peppery nuance and an underlying Bergamot                                     note.                                             3-isobutylthio-2,6-  dimethyl-4-heptanol                                                  ##STR28##       Evaluated at 1% in food grade ethanol, a                                      vegetable, green, horseradish, somewhat                                       rubbery, onion-like aroma containing notes of                                 hyacinth and narcisse.                            3-methylthio-2,6-  dimethyl-4-heptanone                                                   ##STR29##       Evaluated at 1% in food grade ethanol, a                                      sweet, sulfurous, slightly floral and woody                                   aroma with a fruity and berry nuance.              3-(methallylthio)-2,6-  dimethyl-4-heptanone                                             ##STR30##       At 1% in ethanol, a fruity, grapefruit,                                       somewhat floral aroma with underlying yara                                    neroli notes and bready, vegetative nuances.      __________________________________________________________________________

One or more of the aforementioned α-oxy(oxo) sulfides having thestructure: ##STR31## wherein X is one of: ##STR32## R is one of methylor hydrogen, and Y is one of methyl, methallyl, acetyl, 1-propyl, or2-methyl-1-propyl is an olfactory agent and can be incorporated into awide variety of compositions each of which will be enhanced or augmentedby its sweet, green, floral, herbal, vegetative, basil-like, minty,melony, grapefruit, fruity and/or alliaceous notes and/or yara, neroliand/or verdima nuances.

The α-oxy(oxo) sulfides or mixture of α-oxy(oxo) sulfides can be addedto perfume compositions as pure compounds or can be added to mixtures ofmaterials in fragrance-imparting compositions to provide a desiredfragrance character to a finished perfume material. The perfume andfragrance compositions obtained according to this invention are suitablein a wide variety of perfumed articles and can also be used to enhance,modify or reinforce natural fragrance materials. It will thus beappreciated that the α-oxy(oxo) sulfide(s) of our invention is(are)useful as olfactory agent(s) and fragrance(s).

The term "perfume composition" is used herein to mean a mixture ofcompounds, including, for example, natural oils, synthetic oils,alcohols, aldehydes, ketones, esters, lactones, nitriles and frequentlyhydrocarbons which are admixed so that the combined odors of theindividual components produce a pleasant or desired fragrance. Suchperfume compositions usually contain (a) the main note or the "bouquet"or foundation-stone of the composition; (b) modifiers which round-offand accompany the main note; (c) fixatives which include odoroussubstances which lend a particular note to the perfume throughout allstages of evaporation, and substances which retard evaporation and (d)topnotes which are usually low-boiling, fresh-smelling materials. Suchperfume compositions of our invention can be used in conjunction withcarriers, vehicles, solvents, dispersants, emulsifiers, surface-activeagents, aerosol propellants, and the like.

In perfume compositions the individual components contribute theirparticular olfactory characteristics, but the overall effect of theperfume composition will be the sum of the effect of each ingredient.Thus, one or more of α-oxy(oxo) sulfides of our invention can be used toalter, augment, modify or enhance the aroma characteristics of a perfumecomposition or a perfumed aticle, for example, by highlighting ormoderating the olfactory reaction contributed by another ingredient ofthe composition.

The amount of one or more of the α-oxy(oxo) sulfides of our inventionwhich will be effective in perfume compositions depends upon manyfactors, including the other ingredients, their amounts and the effectswhich are desired. It has been found that perfume compositionscontaining as much as 2% or as little as 0.005% by weight of themixtures or compounds of this invention, or even less can be used toimpart a buchu leaf oil-like aroma or a grapefruit oil-like aroma tosoaps, cosmetics and other products. The amount employed will dependupon considerations of cost, nature of the end products, the effectdesired in the finished product, and the particular fragrance sought.

One or more of the α-oxy(oxo) sulfides of our invention as disclosedherein can be used alone, in a fragrance modifying composition, or in aperfume composition as an olfactory component in detergents (anionicdetergents, cationic detergents, and nonionic detergents) and soaps;space deodorants; perfumes; colognes, bath preparations such as bathoil, bath salts; hair preparations such as lacquers, brilliantines,pomades and shampoos; cosmetic preparations such as creams, deodorants,hand lotions, sun screens; powders such as talcs, dusting powders, facepowders and the like. When one or more of the α-oxy (oxo) sulfides ofour invention is used in perfumed articles such as the foregoing, it canbe used in amounts of 0.01% or lower. Generally, it is preferred not touse more than about 2% in the finished perfumed article, since the useof too much will tend to unbalance the total aroma and will needlesslyraise the cost of the article.

The following examples serve to illustrate embodiments of the inventionas it is now preferred to practice it. It will be understood that theseexamples are illustrative and the invention is to be consideredrestricted thereto only as indicated in the appended claims.

EXAMPLE I

(A) PREPARATION OF 3-CHLORO-4-HEPTANONE ##STR33##

Into a 3000 ml, three-necked, round-bottom flask, equipped withmechanical stirrer, 500 ml addition funnel, Y-tube, pot thermometer andgas outlet tube with rubber tubing leading over a stirring solution of10% sodium hydroxide is added 1000g 4-heptanone. Addition of 434 g ofSO₂ Cl₂ drop-wise into the 4-heptanone is commenced while maintainingthe pot temperature in the range of 22°-34° C and is continued over aperiod of two hours. A water aspirator vacuum is applied to the reactionmass in order to pull the acidic gases; sulfur dioxide and hydrogenchloride, over the sodium hydroxide solution.

The reaction mass is periodically sampled using GLC analysis until suchtime as about 25% chlorinated ketone product is found to be present.

While maintaining the reaction mass at 15° C, 1000 ml saturated sodiumchloride is added to the mixture, and the mixture is then stirred for aperiod of 10 minutes. The reaction mass is then transferred to a 5-literseparatory funnel and shaken well, whereupon the organic and aqueousphases separate. The lower aqueous phase (approximately 1000 ml) has apH of about 1. The upper organic phase is washed with 700 ml saturatedsodium bicarbonate solution to a pH of 6-7. The organic phase is thendried over 50 grams anhydrous sodium sulfate and filtered yielding ayellow oil weighing 1063 grams. The organic layer is determined tocontain 24.9% chlorinated ketone and 68.1% original ketone startingmaterial. This material is then vacuum distilled by first adding it to a2000 ml, three-necked, roundbottom flask equipped with a 2.5 × 60 cmvacuum jacketed column packed with 6 mm Raschig Rings, and equipped withan automatic reflux head, a pot thermometer, a heating mantle, a vacuumpump and a dry-ice trap. Fractionation data is as follows:

    ______________________________________                                        Vacuum Pot     Vapor   Weight of                                              (mmHg) Temp.   Temp.   Fraction                                                                              Cut. No.                                                                             Reflux Ratio                            ______________________________________                                        62     80      71      51.0 g  1      60:40                                   62     81.5    71      149.0 g 2      40:60                                   58     82.5    70      157.5 g 3      30:70                                   59     89.5    70      175.0 g 4      30:70                                   59     96      75      110 g   5      30:70                                   59     100     80      24.5 g  6      50:50                                   58     101     90      16.0 g  7      50:50                                   58     102     94      37.5 g  8      30:70                                   55     103     94      144.5 g 9      30:70                                   54     110     95      85.0 g  10     30:70                                   54     119     102     28.0 g  11     30:70                                   15     140     80      45.0 g  12     30:70                                   ______________________________________                                    

GLC analysis on each of cuts 5-12 (conditions 8 feet × 1/4inches SE-30column) yields the following information:

    ______________________________________                                                     Per-    Per-  Per-  Per-  Per-  Per-                                  Per-    cent    cent  cent  cent  cent  cent                                  cent    4-      3-Cl  High  High  High  High                             Cut  low     Hep-    4-Hep-                                                                              Boiler                                                                              Boiler                                                                              Boiler                                                                              Boiler                           No.  Boilers tanone  tanone                                                                              (A)   (B)   (C)   (D)                              ______________________________________                                        5    0.09    96.15    2.97 --    --    --    --                               7            50%     50%                                                      8    --       9.28   87.09 2.43  0.57  --    --                               9    --      trace   95.78 3.22  1.00  --    --                               10   --      --      91.38 4.89  3.34  0.21  --                               11   --      --      69.14 7.27  19.89 3.71  --                               12   --      --       8.32 2.07  49.28 39.69 0.47                             ______________________________________                                    

Cuts 8, 9 and 10 are blended (weight 266.5 gms) and are analyzed asfollows:

    ______________________________________                                        0.95%             4-heptanone                                                 93.89%            3-chloro-4-heptanone                                        3.60%             high boiler A                                               1.57%             high boiler B                                               ______________________________________                                    

EXAMPLE I

B. PREPARATION OF 3-THIOACETYL-4-HEPTANONE

Reaction: ##STR34##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, nitrogen inlet tube, 6 inches Vigreux column with cotton plugand pot thermometer is added a solution of 0.27 grams sodium methoxidein 3 ml anhydrous methanol (0.005 moles sodium methoxide). Under drynitrogen, 0.38 grams of thioacetic acid dissolved in 3 ml anhydrousmethanol (0.005 moles thioacetic acid) is then added to the sodiummethoxide solution over a 2-minute period. A solution of3-chloro-4-heptanone in methanol (0.75 grams 3-chloro-4-heptanonedissolved in one ml anhydrous methanol) prepared according to Part A,supra (cuts 8, 9 and 10 blended) is then added to the reaction masswhich becomes turbid. Stirring is continued for a period of one hour,whereupon GLC analysis (conditions: 8 feet × 1/4 inches SE-30 column)yields the following data:

    ______________________________________                                        15.6%              3-chloro-4-heptanone                                       3.0%               chloro heptanone high boiler                               77.67%             major peak                                                 2.37%              late peak                                                  ______________________________________                                    

With stirring, 15 ml water is added to the reaction mass which thensplits up into two phases, an aqueous phase and an organic phase. The pHof the aqueous phase is 5-6. The organic phase is extracted with two 10ml portions of methylene chloride. The methylene chloride extracts arecombined and washed with 5 ml saturated sodium chloride solution. Theorganic phase is then dried over anhydrous sodium sulfate andconcentrated in a rotary evaporator using water aspirator vacuumyielding 0.65 grams of a dark amber oil. GLC trapping of the major peak(Conditions: 8 feet × 1/4 inches SE-30 column operated at 120° C,programmed at 5° C/minute) yields a compound having a molecular weightof 188 and having a mass spectral analysis, NMR analysis and IR analysiswhich causes confirmation of the structure: ##STR35##

The NMR spectrum is set forth in FIG.1

The infrared spectrum is set forth in FIG. 2.

The NMR analysis is as follows:

    ______________________________________                                         ##STR36##                                                                    0.92 ppm                                                                              (t)     CH.sub.3CH.sub.2                                                                                      6H                                    0.96    (t)     CH.sub.3CCS                                                   2.01-1.44                                                                             (m)     CH.sub.2               4H                                      2.39    (s)                                                                                   ##STR37##                                                                                            5H                                     2.53    (m)                                                                                   ##STR38##                                                    4.20    (t)     OCHCSCO                1H                                     ______________________________________                                    

The IR analysis is as follows: 620 CM⁻¹, 950, 1125, 1350, 1450, 1690,2320, 2870, 2930, 2960.

Material prepared similarly to above example was vacuum distilledyielding 99.3% pure product (boiling point 93.5-94.5° C at 2.8 mm Hg).The thus-distilled material has the same physical properties as setforth above for 3-thioacetyl-4-heptanone.

(C) PREPARATION OF 3-THIOMETHYL-4-HEPTANONE

Reaction: ##STR39##

Into a 50-ml, three-necked, round-bottom flask equipped wth magneticstirrer, dry ice condenser, pot thermometer, cold water bath, refluxcondenser with nitrogen inlet tube and nitrogen bubbler, is placed asolution of 0.54 grams of sodium methoxide in 6 ml anhydrous methanol(0.01 moles sodium methoxide). The sodium methoxide solution is thencooled using the cold-water bath to a temperature of 25° C. The nitrogenflow is ceased and methyl mercaptan in methanol (0.48 grams methylmercaptan in 6 ml anhydrous methanol, 0.01 moles methyl mercaptan) isadded to the reaction mass while maintaining same at 24° C. At 24° C, asolution of 1.49 grams of 3-chloro-4-heptanone in 2 ml anhydrousmethanol (0.01 moles 3-chloro-4-heptanone) is added to the reactionmass. The 3-chloro-4-heptanone is produced according to the process setforth in part (A), supra. The reaction mass is maintained, withstirring, at 25° C for a period of one hour and 15 minutes. At the endof this period, the reaction mass is flushed with nitrogen. The reactionmass is then concentrated on a rotary evaporator using a water aspiratorvacuum to approximately 5 ml.

Distilled water (15 ml) is then added to the concentrated reactionmixture whereupon the reaction mixture forms into two phases; an oilphase and an aqueous phase. the pH of the aqueous phase is in the rangeof 5-6. The oil phase is then extracted with two 12 ml portions ofn-hexane and the phases are separated. The hexane extracts are combined,washed with water (5 ml), dried over anhydrous sodium sulfate, gravityfiltered and concentrated on a rotary evaporator to a weight of 1.29grams. The resulting product contains 90.1% 3-thiomethyl-4-heptanone byGLC having the structure: ##STR40## as confirmed by NMR, IR and massspectral analyses of trapped compound.

The NMR spectrum is set forth in FIG. 3. The IR spectrum is set forth inFIG. 4.

The NMR analysis is as follows:

    ______________________________________                                         ##STR41##                                                                    0.94 ppm                                                                              (t)     CH.sub.3CH.sub.2                                                                                      6H                                    0.97    (t)     CH.sub.3CCS                                                   1.68    (m)     CH.sub.2               4H                                     1.92    (s)     CH.sub.3S              3H                                     2.60    (m)                                                                                    ##STR42##             2H                                     3.08    (t)                                                                                    ##STR43##             1H                                     ______________________________________                                    

The IR analysis is as follows: 1360 cm⁻¹, 1375, 1455, 1690, 2330, 2880,2930, 2960.

Material prepared similarly to above example was vacuum distilledyielding 99.2% pure product (boiling point 78°-78.5° C at 8.5 mm Hg).The thus-distilled material has the same physical properties as setforth above for 3-thiomethyl-4-heptanone.

(D) PREPARATION OF 3-THIOMETHYL-4-HEPTANOL

Reaction: ##STR44##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, nitrogen inlet tube, reflux condenser, pot thermometer and coldwater bath, is added a solution of 0.10 grams sodium borohydride (NaBH₄)dissolved in 4 ml anhydrous ethyl alcohol (0.00265 moles sodiumborohydride). While maintaining the pot temperature at 25° C, a solutionof 0.8 grams of 3-thiomethyl-4-heptanone in 3.5 ml anhydrous ethylalcohol is added to the sodium borohydride-ethanol solution over aone-minute period. The reaction mass then warms up to about 30° C and ismaintained at a temperature of between 25° and 30° C for a period ofabout 1.5 hours. At the end of this period another 0.05 grams (0.00133moles) of sodium borohydride and 2 ml ethanol is added.

After 10 minutes of stirring while maintaining the reaction mass at 25°C, the reaction mass is then worked up as follows: The reaction mixtureis concentrated to about 4 ml of a thick slurry using water aspiratorvacuum. The resulting thick slurry is then combined with 12 ml waterthereby causing the solid to dissolve, and the reaction mass to exist intwo phases; an aqueous phase and an organic phase. The aqueous phase isacidified to a pH of 2-3 using 10% HCl solution. The organic phase isextracted with two 12 ml portions of methylene chloride. The extractsare then combined, washed with 8 ml water, dried over anhydrous sodiumsulfate, gravity filtered, and then concentrated on a rotary evaporator(using water aspirator vacuum) to a weight of 0.58 grams. The desiredproduct is trapped out on an 8 feet × 1/4 inches SE-30 GLC column, andMS, NMR and IR analyses confirm that the resulting compound has thestructure: ##STR45##

The NMR spectrum is set forth in FIG. 5. The infrared spectrum is setforth in FIG. 6.

The NMR analysis is as follows:

    ______________________________________                                        0.94 ppm  (t)        CH.sub.3 -- CH.sub.2 --                                                                       6H                                       1.06      (t)        CH.sub.3 -- C-- C-- S-- -1.51                                                                 (m) -- CH.sub.2 -- 6H                    2.06      (s)        CH.sub.3 -- S-- 3H                                       2.36      (m)        HC-- --                                                                                       2H                                       2.62      (broad)    -- OH                                                    3.52      (m)        HC-- O--        1H                                       ______________________________________                                    

The IR analysis is as follows:

980 cm⁻¹, 1010, 1065, 1370, 1430, 1450, 2320, 2860, 2920, 2960, 3440.

Material prepared similarly to above example was vacuum distilledyielding 99.5% pure product (boiling point 64°-64.5° C at 1.5 mm Hg).The thus-distilled material has the physical properties as set forthabove for 3-thiomethyl-4-heptanol.

EXAMPLE II PREPARATION OF 3-METHALLYLTHIO-2,6-DIMETHYL-4-HEPTANONE

(A) Preparation of 3-chloro-2,6-dimethyl-4-heptanone

Reaction: ##STR46##

Into a one-liter, three-necked, round bottom flask equipped with "Y"tube, pot thermometer, mechanical stirrer, 125 ml addition funnel, gasoutlet tube, cold water bath and water aspirator vacuum is added 356grams of 2,6-dimethyl-4-heptanone (2.4 moles). Over a period of onehour, 67.5 grams (40 ml; 0.5 moles) of SO₂ Cl₂ is slowly added to theketone with stirring while maintaining the reaction mass temperature inthe range of 23°-35° C.

The reaction mass is then evacuated slowly using water aspirator vacuumthereby removing most of the acidic gases resulting from the foregoingreaction.

The reaction mass is then transferred to a one-necked, one-liter,round-bottom flask and the last traces of acidic gases are removed thusyielding 371 grams of product. The reaction mass is then transferred toa 500 ml, three-necked, round-bottom flask equipped with a 2.0 × 30 cmcolumn packed with 1/8 inch helioes, reflux head, magnetic stirrer,heating mantle and vacuum pump and the resulting3-chloro-2,6-dimethyl-4-heptanone is fractionally distilled at a vaportemperature of 106°-107° C and a pressure of 45-46 mm Hg yielding aproduct of 97% purity as confirmed by GLC, mass spectral, NMR and IRanalyses.

B. PREPARATION OF 3-MERCAPTO-2,6-DIMETHYL-4-HEPTANONE

Reaction: ##STR47##

Into a 250 ml, round-bottom, three-necked flask equipped with magneticstirrer, pot thermometer, 6 inches Vigreux distillation column with gasoutlet at top leading over 200 ml 10% sodium hydroxide solution, H₂ Sgas inlet tube (sub-surface), "Y" tube, 50 ml addition funnel, gasbubbler, and dry ice-isopropyl alcohol bath, and cold water bath isadded a solution of 11.6 grams of sodium methoxide dissolved in 90 mlanhydrous methanol. The sodium methoxide solution is cooled to atemperature of -15° C using the dry ice-isopropanol bath. Whilemaintaining the temperature of the sodium methoxide solution at -10 to-5° C, hydrogen sulfide is bubbled into the reaction mass over a periodof 2 hours. While continuing to bubble in hydrogen sulfide andmaintaining the reaction mass at a temperature in the range of -5° C to-9° C, the 3-chloro-2,6-dimethyl-4-heptanone prepared in Part A of thisexample (18.2 grams; 0.100 moles) is added slowly to the reaction massfrom the addition funnel over a period of 13 minutes. The reaction massis then maintained at a temperature of 0° C-26° C for a period of 4hours (25° C-26° C for the last 1.5 hours).

The reaction mass is then concentrated to approximately 25 ml (thickslurry) using a rotary evaporator and water aspirator vacuum. 85 mldistilled water is then added to the reaction mass, with stirring, whilemaintaining the temperature at 25° C, thereby yielding a turbid yellowsolution. 85 grams of 10% aqueous sodium hydroxide is then added to theresulting mixture whereupon the temperature rises from 25° C to 28° C(pH = 10-11). The basic aqueous solution is then extracted with two 70ml portions of methylene chloride and the extracts are combined, driedand concentrated yielding 1.7 grams of an oil. The basic aqueoussolution is then acidified with 115 ml 10% hydrochloric acid to a pH of1-2. This is then extracted with four 50 ml portions of methylenechloride. The methylene chloride extracts are combined and washed withtwo 35 ml portions of saturated sodium chloride (to a pH of 5) and driedover anhydrous sodium sulfate. The resulting mixture is gravity filteredand concentrated on a rotary evaporator to yield 15.5 grams of productcontaining 96.1% 3-mercapto-2,6-dimethyl-4-heptanone as confirmed bymass spectral, NMR and IR analyses. This material is vacuum distilled ata vapor temperature of 77.5°-78° C and a pressure of 6 mm Hg.

C. Preparation of 3-methallylthio-2,6-dimethyl-4-heptanone

Reaction: ##STR48##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, "Y" tube, nitrogen inlet, reflux condenser with cotton plug,cold water bath and warm water bath is added a solution of 0.162 gramsof sodium methoxide dissolved in 2 ml anhydrous methanol. Over a periodof 1 minute is added a solution of 0.522 grams of3-mercapto-2,6-dimethyl-4-heptanone dissolved in 3 ml anhydrousmethanol, with stirring. After stirring 12 minutes at 24°-25° C, asolution of 0.3 grams of 3-chloro-2-methyl propene in 1 ml anhydrousmethanol is added. With a water bath, the resulting reaction mass iswarmed to 31° C and the reaction mass is then stirred while maintainingthe temperature in the range of 23-30° C for a period of 2 hours.

The reaction mass is then concentrated on a rotary evaporator usingwater aspirator vacuum to approximately 4 ml yielding a slurry. To theslurry is added 8 ml water and the solid dissolves. The reaction mass isthen acidified to a pH of 1-2 with 3 drops of 10% hydrochloric acid. Thereaction mass is then extracted with three 8 ml portions of methylenechloride and the extracts are combined, washed with 10 ml water, driedover anhydrous sodium sulfate and gravity filtered. The extracts areconcentrated on a rotary evaporator to yield 0.54 grams of a white oilcontaining 93.6% by GLC of 3-methallylthio-2,6-dimethyl-4-heptanone asconfirmed by MS, IR and NMR analyses of trapped product.

The NMR spectrum is set forth in FIG. 7. The infrared spectrum is setforth in FIG. 8.

The mass spectral analysis is as follows:

    ______________________________________                                        M/E             Relative Intensity                                            ______________________________________                                        41              29                                                            55              44.sup.3                                                      57              37.sup.6                                                      69              10                                                            85              43.sup.5                                                      87              93.sup.2                                                      109             33                                                            142             44.sup.4                                                      143             100.sup.1                                                     M 228           28                                                            ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        1.92 ppm, 2.06                                                                            (2 doublets)                                                                              ##STR49##     12H                                     1.78        (s)        CCH.sub.3      3H                                      2.12        (m)        methine protons                                                                              2H                                      2.47        (t)        CH.sub.2       2H                                      2.82        (d)                                                                                       ##STR50##     1H                                      3.01        (s)        CCH.sub.2S     2H                                      4.86        (s)                                                                                       ##STR51##                                             ______________________________________                                    

The IR analysis is as follows: 890 cm⁻¹, 1035, 1160, 1200, 1225, 1285,1360, 1380, 1400, 1460, 1640, 1695, 2870, 2960, 3080.

Material prepared similarly to above example was vacuum distilledyielding 99.8% pure product (boiling point 100°-105° C at 1.3 mm Hg).The thus-distilled material has the same physical properties as setforth above for 3-methallylthio-2,6-dimethyl-4-heptanone.

EXAMPLE II

D. PREPARATION OF 3-THIOACETYL-2,6-DIMETHYL-4-HEPTANONE

Reaction: ##STR52##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, nitrogen inlet tube at top of 6 inches Vigreux column, refluxcondenser with cotton plug, pot thermometer, water bath and heatingmantle is placed a solution containing 0.27 grams of sodium methoxide(0.005 moles) in 3 ml anhydrous methanol. To the sodium methoxidesolution is added a solution of 0.38 grams (0.005 moles) of thioaceticacid in 3 ml anhydrous methanol, with stirring, while maintaining thereaction mass temperature in the range of 23°-25° C. The addition takesplace over a period of 10 minutes. While maintaining the reaction masstemperature at 23° C, a solution of 0.883 grams (0.005 moles) of3-chloro-2,6-dimethyl-4-heptanone (prepared according to Part A) in 2 mlanhydrous methanol is added to the reaction mass. While maintaining thereaction mass temperature between 35° and 45° C and over a period of 3hours, the reaction mass is stirred. At the end of the 3-hour periodonly 6% of product is formed. The reaction mass is then refluxed at66°-76° C for a period of 12 hours, at which point it is indicated byGLC, NMR, IR and mass spectral analyses that3-thioacetyl-2,6-dimethyl-4-heptanone is formed in an amount of 65%.

The reaction mass is then concentrated on a rotary evaporator usingwater aspirator vacuum to 4 ml of an oily product. Ten ml water is thenadded, and the solid dissolves. The oil layer is extracted with three 8ml portions of methylene dichloride, and the extracts are combined andwashed with one 8 ml water portion. The extracts are then dried overanhydrous sodium sulfate, gravity filtered and concentrated yielding0.54 grams of a yellow oil. The desired product is trapped on a GLCSE-30 column (Conditions: 8 feet × 1/4inches).

The NMR analysis is as follows:

    ______________________________________                                        1.01-0.88 ppm Methyl protons        12H                                       2.42-2.03     Methine protons                                                  2.44                                                                                        ##STR53##             7H                                       2.40                                                                                         ##STR54##                                                      4.14                                                                                         ##STR55##                                                      ______________________________________                                    

The infrared analysis is as follows: 6.20 cm⁻¹, 950, 1100, 1130, 1360,1380, 1465, 1695, 2870, 2930, 2960.

The mass spectral analysis is as follows:

    ______________________________________                                        M/E             Relative Intensity                                            ______________________________________                                        41              14.sup.5                                                      43              40.sup.3                                                      55              12                                                            57              60.sup.2                                                      85              100.sup.1                                                     89              27.sup.4                                                      131             12.sup.6                                                      141             9                                                             173             11                                                            M 216           7                                                             ______________________________________                                         7                                                                        

The NMR spectrum is set forth in FIG. 8(A). The infrared spectrum is setforth in FIG. 8(B).

EXAMPLE III

A. Preparation of 3-propylthio-4-heptanone ##STR56##

Into a 50 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, nitrogen inlet tube, pot thermometer and coldwater bath, is placed a solution of 0.54 grams of sodium methoxidedissolved in 6 ml anhydrous methanol (0.01 moles of sodium methoxide).The sodium methoxide solution is cooled using the water bath to 25° C. Asolution of 0.76 grams of n-propyl mercaptan dissolved in 6 ml anhydrousmethanol (0.01 moles n-propyl mercaptan) is then added to the sodiummethoxide/methanol solution, and the temperature rises to 28° C. 1.5 g(0.01 moles) 3-chloro-4-heptanone dissolved in 2 ml anhydrous methanolis then added, and the temperature of the reaction mass rises to 38° C,whereupon it is cooled using the water bath to a temperature in therange of 25°-30° C. The reaction mass is then stirred under nitrogen fora period of 6 hours.

The reaction mass is then concentrated to a volume of 4 ml using arotary evaporator to which water aspirator vacuum is applied. 9 mldistilled water is then added to the reaction mass concentrate whereuponthe solid dissolves. The oil phase is extracted with three 8 ml portionsof methylene chloride, and the extracts are combined and washed with 8ml of water and dried over anhydrous sodium sulfate and filtered andthen concentrated. GLC, MS, NMR and IR analyses of trapped product yieldthe information that the subject material is 3-propylthio-4-heptanone

The NMR spectrum is set forth in FIG. 9. The IR spectrum is set forth inFIG. 10.

The NMR analysis is as follows:

    ______________________________________                                        0.87-1.04 ppm                                                                            superimposed                                                                              CH.sub.3        9H                                                signals                                                            1.63       (m)         CH              6H                                     2.38       (t)         CH.sub.2S       2H                                     2.60       (t)                                                                                        ##STR57##      2H                                     3.11       (t)         OCHCS           1H                                     ______________________________________                                    

The IR analysis is as follows: 1130 cm⁻¹, 1165, 1290, 1360, 1380, 1405,1460, 1700, 2880, 2940, 2960.

The mass spectral analyses is as follows:

    ______________________________________                                        M/E             Relative Intensity                                            ______________________________________                                        41              20.sup.4                                                      43              26.sup.3                                                      55              5                                                             71              10                                                            75              35.sup.2                                                      117             10                                                            118             100.sup.1                                                     118             10.sup.6                                                      119             9                                                             M 188           16.sup.5                                                      ______________________________________                                    

Material prepared similarly to above example was vacuum distilledyielding 98.4% pure product (boiling point 72°-73° C at 1.5 mm Hg). Thethus-distilled material has the same physical properties as set forthabove for 3-propylthio-4-heptanone.

B. Preparation of 3-propylthio-4-heptanol

Reaction: ##STR58##

Into a 25 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, pot thermometer, and nitrogen inlet (forflushing with dry nitrogen) is added a solution of 0.15 grams of sodiumborohydride dissolved in 6 ml anhydrous methanol (0.004 moles sodiumborohydride). With stirring, a solution of 1.0 grams of3-propylthio-4-heptanone dissolved in 4 ml anhydrous ethyl alcohol isadded to the sodium borohydride solution which then warms to 28° C. Thereaction mass is stirred for a period of 2 hours at 25° C and thenconcentrated on a rotary evaporator (using water aspirator vacuum) to avolume of 4 ml yielding an oily solid. 8 ml water is then added to thesolid, with stirring, and the solid dissolves yielding two phases: anoil phase and a water phase. The resulting reaction mass is acidifiedwith 10% hydrochloric acid to a pH of between 2 and 3. The oil phase isextracted with three 8 ml volumes of methylene chloride, and theextracts are combined and washed with 8 ml water. The extracts are thendried over anhydrous sodium sulfate, filtered and concentrated to aweight of 0.79 grams (water-white oil). GLC, IR, mass spectral and NMRanalyses after GLC trapping (conditions: 8 feet × 1/4 inch SE-30 column)yield the information that the crude material is 96% product having thestructure of 3-propylthio-4heptanol.

The NMR spectrum is set forth in FIG. 11. The IR spectrum is set forthin FIG. 12.

The NMR analysis is as follows:

    ______________________________________                                        1.13-0.96 ppm                                                                           superimposed                                                                             methyl protons  9H                                                 signals                                                             1.44      (m)        -- CH.sub.2 --  8H                                       2.47      (s)        --OH                                                                                          4H                                       2.49      (m)        HC-- S-- CH.sub.2 --                                     3.50      (m)        HC-- O--        1H                                       ______________________________________                                    

The IR analysis is as follows: 1290 cm⁻¹, 1380, 1460, 2880, 2940, 2970,3460.

Material prepared similarly to above example was vacuum distilledyielding 99.8% pure product (boiling point 65° C at 0.4 mm Hg). Thethus-distilled material has the same physical properties as set forthabove for 3-propylthio-4-heptanol.

EXAMPLE IV PREPARATION OF 3-ISOBUTYLTHIO-4-HEPTANONE

Reaction: ##STR59##

Into a 50 ml, three-necked, round bottom flask equipped with magneticstirrer, reflux condenser, pot thermometer, water bath, 15 cm Vigreuxcolumn with nitrogen inlet at top is added a solution of 0.54 grams ofsodium methoxide (0.01 moles) in 6 ml anhydrous methanol. The reactionmass is cooled to 25° C and a solution of 0.90 grams of isobutylmercaptan (2-methyl-1-propanethiol) dissolved in 6 ml anhydrous methanolis added over a period of one minute. After keeping the reaction mass at24° C with stirring for a period of 10 minutes, 1.50 grams of3-chloro-4-heptanone dissolved in 2 ml anhydrous methyl alcohol (0.01moles of 3-chloro-4-heptanone) is added to the reaction mass which thenwarms to 37° C. The reaction mass is allowed to cool to a temperature of24° C and stirred at that temperature for a period of 6 hours.

The reaction mass is then concentrated on a rotary evaporator usingwater aspirator vacuum to a volume of 4 ml yielding an oily solid. Tenml water is then added, and the solid dissolves yielding two phases: anoil phase and an aqueous phase. The oil phase is extracted with three 9ml portions of methylene chloride, and the extracts are combined andwashed with 9 ml water. The extracts are then dried over anhydroussodium sulfate, filtered and concentrated to a weight of 1.78 grams.

Mass spectral, infrared, NMR and IR analyses yield the information thatthe reaction mass contains 90.9% product which is3-isobutylthio-4-heptanone.

The NMR spectrum is set forth in FIG. 13. The IR spectrum is set forthin FIG. 14.

The NMR analysis is as follows:

    ______________________________________                                        0.96 ppm  (d)                                                                                     ##STR60##                                                 0.98      (t)      CH.sub.3CH.sub.2   12H                                     0.91      (t)                                                                                     ##STR61##                                                 1.70      (m)                                                                                     ##STR62##         5H                                      2.26      (d)      SCH.sub.2          2H                                      2.60      (t)                                                                                     ##STR63##         2H                                      3.10      (t)      OCHCS              1H                                      ______________________________________                                    

The IR analysis is as follows: 1365 cm⁻¹, 1380, 1460, 1700, 2880, 2940,2960.

EXAMPLE V

A. PREPARATION OF 3-ISOBUTYLTHIO-2,6-DIMETHYL-4-HEPTANONE

Reaction: ##STR64##

Into a 50 ml, three-necked, round bottom flask equipped with potthermometer, magnetic stirrer, gas inlet tube (for nitrogen) at top of15 cm Vigreux column, nitrogen bubbler and cold water bath is added asolution of 0.54 grams (0.01 moles) of sodium methoxide dissolved in 6ml anhydrous methanol. The solution is cooled to 24° C and a solution of0.90 grams (0.01 moles) of isobutyl mercaptan dissolved in 6 mlanhydrous methanol is then added to the reaction mass. After stirring at24° C for a period of 10 minutes, a solution of 1.77 grams of3-chloro-2,6-dimethyl-4-heptanone dissolved in 2 ml anhydrous methanolis added to the reaction mass with stirring at 24° C-25° C. The reactionmass is then stirred for a period of 8 hours.

The reaction mass is then concentrated on a rotary evaporator usingwater aspirator vacuum to 5 ml of a thick oil/solid slurry. 15 ml wateris added and the solid dissolves. The resulting liquid mixture being in2 phases; an aqueous phase and an organic phase. The reaction mass isthen extracted with three 10 ml portions of methylene dichloride and theextracts are combined and washed with 8 ml water. The extracts are thendried over anhydrous sodium sulfate, gravity filtered and concentratedon a rotary evaporator to a weight of 1.89 grams (pale yellow oil). GLC,NMR, IR and mass spectral analyses yield the information that theresulting product is 79.2% 3-isobutylthio-2,6-dimethyl-4-heptanone.

The NMR analysis is as follows:

    ______________________________________                                        0.94 ppm, 1.10 methyl protons 18 H                                            2.26-1.60      methine protons                                                                              3 H                                             2.26                                                                                          ##STR65##     2 H                                             2.50           CH.sub.2C      2 H                                             2.80                                                                                          ##STR66##     1 H                                             ______________________________________                                    

The IR analysis is as follows: 1035 cm⁻¹, 1160, 1285, 1360, 1380, 1460,1700, 2870, 2930, 2960.

The mass spectral analysis is as follows:

    ______________________________________                                        M/E               Relative Intensity                                          ______________________________________                                        29                7                                                           41                11.sup.5                                                    55                17.sup.4                                                    57                42.sup.2                                                    69                6                                                           85                8                                                           89                33.sup.3                                                    145               100.sup.1                                                   146               9.sup.6                                                     M 230             8                                                           ______________________________________                                    

The NMR spectrum is set forth in FIG. 14(A). The IR spectrum is setforth in FIG. 14(B).

B. PREPARATION OF 3 -ISOBUTYLTHIO-2,6-DIMETHYL-4-HEPTANOL

Reaction: ##STR67##

Into a 25 ml, three-necked, round-bottom flask equipped with magneticstirrer, reflux condenser, pot thermometer and nitrogen inlet tube toflush with dry nitrogen, is added a solution of 0.1 grams (0.00265moles) of sodium borohydride dissolved in 4 ml anhydrous ethanol. Whilethe temperature of the sodium borohydride solution is at 24° C, asolution of 1.1 grams of 3-isobutylthio-2,6-dimethyl-4-heptanone(prepared according to Part A) dissolved in 4 ml anhydrous ethanol isadded to the reaction mass slowly. The reaction mass is then stirred fora period of 6.5 hours.

The reaction then shows 30% product(3-isobutylthio-2,6-dimethyl-4-heptanol) by GLC analysis. An additional0.2 grams of sodium borohydride dissolved in 6 ml anhydrous ethanol isadded, and the reaction mass is continued to be stirred for a period of4 hours. GLC analysis shows 59% product. Another 0.15 grams of sodiumborohydride in 5 ml anhydrous ethanol is added and stirred for anadditional 4 hours.

GLC analysis then shows 78% product.

The reaction mixture is then concentrated on a rotary evaporator usingwater aspirator vacuum to 5 ml of an oily solid. 6 ml water is thenadded and the solid dissolves yielding two liquid phases; an organicphase and an aqueous phase. The reaction mass is neutralized with 10%HCl to a pH of 5. The oil is then extracted with 20 ml methylenedichloride, and the extracts are washed with water. The extracts arethen dried over anhydrous sodium sulfate, filtered and concentrated on arotary evaporator to a weight of 0.82 grams (pale yellow oil). GLCanalysis indicates that the material is 86.4% product. NMR and IRanalyses of GLC trapped compound yield the information that the productis 3-isobutylthio-2,6-dimethyl-4-heptanol.

The NMR spectrum is set forth in FIG. 15. The IR spectrum is set forthin FIG. 16.

The NMR analysis is as follows:

    ______________________________________                                        1.10-          superimposed                                                                             CH.sub.3      18H                                   0.89 ppm       signals                                                        1.34   (m)                methine       3H                                                              protons                                             1.84   (m)                CH.sub.2CO    2H                                    2.44   (m)                CH.sub.2S, HCS                                                                              3H                                    2.79   (broad)            OH            1H                                    3.72   (m)                                                                                               ##STR68##    1H                                    ______________________________________                                    

The IR analysis is as follows: 1055 cm⁻¹, 1365, 1385, 1465, 2880, 2930,2960, 3460.

EXAMPLE VI PREPARATION OF 3-METHYLTHIO-2,6-DIMETHYL-4-HEPTANONE

Reaction: ##STR69##

Into a 50 ml, three-necked, round-bottom flask equipped with potthermometer, magnetic stirrer, gas inlet tube (subsurface), gas bubbler,methyl mercaptan gas cylinder, 15 cm Vigreux column, gas outlet tubeleading to stirred 10% sodium hydroxide solution, and cold water bath isadded a solution of 0.54 grams of sodium methoxide in 12 ml anhydrousmethanol (0.01 moles sodium methoxide). The reaction mass warms to 30°C, and it is cooled to 23° C using the cold water bath. Over a period of20 minutes the methyl mercaptan is bubbled in below the surface of theliquid while maintaining the temperature of the reaction mass at 22°-23°C. The reaction flask is then flushed with dry nitrogen, and a solutionof 1.77 grams of 3-chloro-2,6-dimethyl-4-heptanone dissolved in 2 mlanhydrous methanol is then added to the reaction mass. The reaction massremains at 23°-25° C and is stirred at that temperature for a period of2.5 hours. GLC analysis indicates 79% product. The reaction mass is thenwarmed to 35° C and maintained at 28°-35° C for another 1.5 hours.

The reaction mass is then concentrated to a volume of 5 ml using arotary evaporator to which water aspirator vacuum is applied. 15 mldistilled water is then added to dissolve the solid yielding a two phasemixture (an aqueous phase and an organic phase). The reaction mass isthen extracted with three 10 ml portions of methylene chloride, and theextracts are combined and washed with 10 ml of water. The combinedextracts are then dried over anhydrous sodium sulfate, gravity filteredand concentrated on a rotary evaporator to a weight of 1.56 grams. GLC,MS, NMR and IR analyses yield the information that the resultingmaterial is 89.6% product, 3-methylthio-2,6-dimethyl-4-heptanone. Thepure material is trapped out using preparative GLC (conditions: 8 feet ×1/4 inch SE-30 column).

The NMR spectrum is set forth in FIG. 17. The IR spectrum is set forthin FIG. 18.

The Mass Spectral analysis is as follows:

    ______________________________________                                        M/E               Relative Intensity                                          ______________________________________                                        41                8.sup.5                                                     55                32.sup.2                                                    57                12.sup.3                                                    61                5                                                           69                5                                                           85                7.sup.6                                                     102               6                                                           103               100.sup.1                                                   104               6                                                           M 188             10.sup.4                                                    ______________________________________                                    

The NMR analysis is as follows:

    ______________________________________                                        0.94, 1.08 ppm Methyl protons  12 H                                           1.90           CH.sub.3S       3 H                                            2.37 - 1.96    Methine protons 2 H                                            2.49                                                                                          ##STR70##                                                     2.78                                                                                          ##STR71##                                                     ______________________________________                                    

The IR analysis is as follows: 1035 cm⁻¹, 1160, 1360, 1380, 1400, 1465,1695, 2870, 2920, 2960

EXAMPLE VII OTTO OF ROSE PERFUME FORMULATION

The following mixture is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                        Phenyl acetic acid       5                                                    Hydroxycitronellal       10                                                   Geraniol                 125                                                  Citronellol              150                                                  Phenyl ethyl alcohol     50                                                   Phenyl ethyl acetate     4                                                    Ethyl phenyl acetate     5                                                    Citronellyl formate      20                                                   Geranyl acetate          25                                                   Linalool                 15                                                   Terpineol                10                                                   Eugenol                  3                                                    Phenyl acetaldehyde dimethyl acetal                                                                    5                                                    Benzyl acetate           3                                                    Guaiacwood Oil           5                                                    3-methylthio-4-heptanone produced according                                   to the process of Part "C" of Example I                                                                10                                                   ______________________________________                                    

The 3-methylthio-4-heptanone, produced according to the process of Part"C" of Example I imparts a green, fruity, spicy topnote socharacteristic of rose otto to this formulation.

EXAMPLE VIII ORIENTAL VETIVERT

The following mixture is prepared:

    ______________________________________                                        Ingredients              Parts by Weight                                      ______________________________________                                        Orange oil Florida       150                                                  Lemon Oil                75                                                   Oil of bitter orange     100                                                  Grapefruit oil           200                                                  Neroli oil               20                                                   Isocyclemone E (a product produced                                            according to the process of Example VI                                        of U.S. Pat. No. 3,907,321, issued on                                         Sept. 23, 1975, which comprises reacting                                      myrcene with 3-methyl-3-pentent-2-one in                                      the presence of aluminum chloride and                                         then cyclizing the resulting Diels-Alder                                      adduct.)                 40                                                   Gamma methyl ionone      15                                                   Ylang extra              5                                                    Auralva (The Shiff base of methyl anthranilate                                and hydroxy citronellal, specifically                                         described in Section 1735 of Arctancer,                                       "Perfume and Flavor Chemicals (Aroma                                          Chemicals)" 1969)        15                                                   Lyral 4-(4-methyl,4-hydroxyamyl) .increment..sup.3 -                          cyclohexene carboxaldehyde                                                                             30                                                   Grisalva (produced by the 50% sulfuric acid                                   treatment of 3-ethyl-1 2,2,6-trimethyl-                                       cyclohexene-5-yl-l!hexene-3-ol-6)                                                                      10                                                   3-(methallythio)-2,6-dimethyl-4-heptanone,                                    produced according to the process of                                          Example II(C).           50                                                   ______________________________________                                    

The 3-(methyallylthio)-2,6-dimethyl-4-heptanone, produced according tothe process of Example II(C) imparts a sweet, orange-flower, green betavetivone woody character to this composition.

EXAMPLE IX NARCISSE FORMULATION

The following mixture is prepared:

    ______________________________________                                        Ingredient               Parts by Weight                                      ______________________________________                                        Benzyl alcohol           50                                                   Benzyl benzoate          25                                                   Terpineol                30                                                   Nerol                    15                                                   Phenyl ethyl alcohol     50                                                   Geraniol                 40                                                   Linalool                 50                                                   Para cresyl phenyl acetate                                                                             10                                                   Benzyl acetate           6                                                    Acetyl isoeugenol        20                                                   Heliotropin              30                                                   Ylang extra              5                                                    Para cresol              1                                                    3-methylthio-4-heptanol, produced according                                   to the process of Example I, Part "D"                                                                  20                                                   ______________________________________                                    

The 3-methylthio-4-heptanol, produced according to the process ofExample I, Part "D" imparts a green, floral, heady tobacco-like orientalmiddle and undertone necessary for narcisse.

EXAMPLE X COMPARISON OF SUBSTITUTED THIOHEPTANONES AND THEIRCORRESPONDING ALCOHOLS

3-methylthio-4-heptanone (hereinafter referred to as "chemical I") has apowerful green, minty, herbaceous odor.

3-methylthio-4-heptanol (hereinafter referred to as "chemical II") has agreen, floral, herbal odor, about one-fifth the strength of chemical I.

3-(methallylthio)2,6-dimethyl-4-heptanone (hereinafter referred to as"chemical III") has a floral, herbaceous aroma with a fruity, grapefruit(nootkatone) character.

The foregoing materials, chemicals I, II and III may be used inperfumery to give unusual and novel effects to various fragrance types.They are useful in creating modern blends which are in some cases farremoved from the classical concepts of perfumery. The use of chemicalsI, II and III may be demonstrated in the following modern herbalformulation:

    ______________________________________                                        Ingredients          A       B       C                                        ______________________________________                                        Oakmoss Absolute 50% in diethyl-                                              phthalate            20      20      20                                       α-methyl-3,4-methylene-dioxy-                                           hydrocinnamic aldehyde                                                                             10      10      10                                       methyl dihydrojasmonate (produced                                             by Firmenich et Cie of Geneva,                                                Switzerland)         100     100     100                                      Coumarin             20      20      20                                       Musk Ketone          80      80      80                                       Isocyclocitral (10% in                                                        diethylphthalate)    10      10      10                                       Galbanum Oil (10% in diethyl-                                                 phthalate)           6       6       6                                        Rosemary Oil         10      10      10                                       Pine Needle Oil      60      60      60                                       Fir Balsam Absolute (10% in                                                   diethylphthalate)    10      10      10                                       Bergamot Oil         60      60      60                                       Lemon Oil            14      14      14                                       Benzyl Acetate       468     460     460                                      Linalool             80      80      80                                       Indol (10% in diethylphthalate)                                                                    6       6       6                                        Undecalactone (10% in diethyl-                                                phthalate)           12      12      12                                       Ylang Ylang Oil      32      32      32                                       Alkylthio chemical I 2       --      --                                       Alkythio chemical II --      10      --                                       Alkythio chemical III                                                                              --      --      10                                       ______________________________________                                    

The addition of 0.2% by weight of chemical I gives increased strength tothe fragrance as well as modifying the herbal character and rendering itunusual and novel. The material can be used in perfumery at fromapproximately 1 ppm (0.0001%) up to approximately 1%.

The weaker alcohol, chemical II, is added to the fragrance at 1% byweight. The addition of this material gives a softer effect but altersthe herbal effect to an unusual and novel character. Chemical II may beused in perfumery from approximately 0.01% to 5% by weight. For specialeffects up to 50% may be used.

The addition of 1% of chemical III gives quite a different effect. Inthis case the herbal character is not altered as in the other examples,but the citrus notes are enhanced and strengthened. This chemical may beused in perfumery from approximately 0.01% to 10% by weight. For specialeffects up to 50% may be used.

In all cases of the above examples, the fragrance is improved by theaddition of the alkylthio chemicals I, II and III and rendered moredesirable and novel.

EXAMPLE XI PREPARATION OF SOAP COMPOSITIONS

100 grams of soap chips are mixed with 1 gram of the chemical set forthin Table II below until a substantially homogeneous composition isobtained. The perfumed soap composition manifests an aroma according tothe aroma set forth in Table II below:

                  Table II                                                        ______________________________________                                        Compound       Aroma                                                          ______________________________________                                        3-methylthio-4-heptanol                                                                      A sweet, green, floral, herbal,                                               vegetative aroma with an                                                      underlying verdima nuance.                                     3-methylthio-4-heptanone                                                                     A green, minty, herbaceous aroma                                              with basil nuances.                                            3-propylthio-4-heptanol                                                                      A green aroma with floral nuances.                             3-thioacetyl-2,6-dimethyl-                                                                   A grapefruit oil-like aroma.                                   4-heptanone                                                                   3-isobutylthio-4-heptanone                                                                   A green, spicey and peppery                                                   aroma with an underlying bergamot                                             note.                                                          3-isobutylthio-2,6-dimethyl-                                                                 A green aroma containing notes                                 4-heptanol     of hyacinth and narcisse.                                      3-methylthio-2,6-dimethyl-                                                                   A sweet, slightly floral and                                   4-heptanone    woody aroma with fruity and                                                   berry nuances.                                                 3-(methallythio)-2,6-                                                                        A fruity, grapefruit, somewhat                                 dimethyl-4-heptanone                                                                         floral aroma with underlying                                                  yara and neroli notes and                                                     bready, vegetative nuances.                                    ______________________________________                                    

EXAMPLE XII PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder (a non-ionic detergent powdercontaining a proteolytic enzyme prepared according to Example I ofCanadian Pat. No. 985,190 issued on Mar. 9, 1976) is mixed with 0.15grams of the α-oxy(oxo) sulfides set forth in Table III below until asubstantially homogeneous composition is obtained. This composition hasan excellent aroma as defined in Table III below:

    ______________________________________                                        Compound       Aroma                                                          ______________________________________                                        3-methylthio-4-heptanol                                                                      A sweet, green, floral, herbal,                                               vegetative aroma with an                                                      underlying verdima nuance.                                     3-methylthio-4-heptanone                                                                     A green, minty, herbaceous aroma                                              with basil nuances.                                            3-propylthio-4-heptanol                                                                      A green aroma with floral nuances.                             3-thioacetyl-2,6-dimethyl-                                                                   A grapefruit oil-like aroma.                                   4-heptanone                                                                   3-isobutylthio-4-heptanone                                                                   A green, spicey and peppery                                                   aroma with an underlying bergamot                                             note.                                                          3-isobutylthio-2,6-dimethyl-                                                                 A green aroma containing notes                                 4-heptanol     of hyacinth and narcisse.                                      3-methylthio-2,6-dimethyl-                                                                   A sweet, slightly floral and                                   4-heptanone    woody aroma with fruity and                                                   berry nuances.                                                 3-(methallylthio)-2,6-                                                                       A fruity, grapefruit, somewhat                                 dimethyl-4-heptanone                                                                         floral aroma with underlying                                                  yara and neroli notes and                                                     bready, vegetative nuances.                                    ______________________________________                                    

EXAMPLE XIII PREPARATION OF COSMETIC POWDER COMPOSITIONS

Cosmetic powders are prepared by mixing in a ball mill 100 grams oftalcum powder with 0.25 grams of each of the compounds set forth inTable IV below. Each of these powders has an excellent aroma as setforth in Table IV below.

                  Table IV                                                        ______________________________________                                        Compound       Aroma                                                          ______________________________________                                        3-methylthio-4-heptanol                                                                      A sweet, green, floral, herbal,                                               vegetative aroma with an                                                      underlying verdima nuance.                                     3-methylthio-4-heptanone                                                                     A green, minty, herbaceous aroma                                              with basil nuances.                                            3-propylthio-4-heptanol                                                                      A green aroma with floral nuances.                             3-thioacetyl-2,6-dimethyl-                                                                   A grapefruit oil-like aroma.                                   4-heptanone                                                                   3-isobutylthio-4-heptanone                                                                   A green, spicey and peppery                                                   aroma with an underlying bergamot                                             note.                                                          3-isobutylthio-2,6-dimethyl-                                                                 A green aroma containing notes                                 4-heptanol     of hyacinth and narcisse.                                      3-methylthio-2,6-dimethyl-                                                                   A sweet, slightly floral and                                   4-heptanone    woody aroma with fruity and                                                   berry nuances.                                                 3-(methallythio)-2,6-                                                                        A fruity, grapefruit, somewhat                                 dimethyl-4-heptanone                                                                         floral aroma with underlying                                                  yara and neroli notes and                                                     bready, vegetative nuances.                                    ______________________________________                                    

EXAMPLE XIV PERFUMED LIQUID DETERGENTS

Concentrated liquid detergents with rich, pleasant aromas as set forthin Table V below are prepared containing 0.10%, 0.15% and 0.20% of anα-oxy(oxo) sulfide as set forth in Table V below. They are prepared byadding and homogeneously admixing the appropriate quantity of α-oxy(oxo)sulfide in the liquid detergent. The liquid detergents are all producedusing anionic detergents containing a 50:50 mixture of sodium lauroylsarcosinate and potassium N-methyl lauroyl tauride. The detergents allpossess a pleasant fragrance as defined in the table below, theintensity increasing with greater concentration of α-oxy(oxo) sulfide ofthis invention.

    ______________________________________                                        Compound       Aroma                                                          ______________________________________                                        3-methylthio-4-heptanol                                                                      A sweet, green, floral, herbal,                                               vegetative aroma with an                                                      underlying verdima nuance.                                     3-methylthio-4-heptanone                                                                     A green, minty, herbaceous aroma                                              with basil nuances.                                            3-propylthio-4-heptanol                                                                      A green aroma with floral nuances.                             3-thioacetyl-2,6-dimethyl-                                                                   A grapefruit oil-like aroma.                                   4-heptanone                                                                   3-isobutylthio-4-heptanone                                                                   A green, spicey and peppery                                                   aroma with an underlying bergamot                                             note.                                                          3-isobutylthio-2,6-dimethyl-                                                                 A green aroma containing notes                                 4-heptanol     of hyacinth and narcisse.                                      3-methylthio-2,6-dimethyl-                                                                   A sweet, slightly floral and                                   4-heptanone    woody aroma with fruity and                                                   berry nuances.                                                 3-(methallythio)-2,6-                                                                        A fruity, grapefruit, somewhat                                 dimethyl-4-heptanone                                                                         floral aroma with underlying                                                  yara and neroli notes and                                                     bready, vegetative nuances.                                    ______________________________________                                    

EXAMPLE XV

an α-oxy(oxo) sulfide as set forth in Table VI below is incorporated ina cologne at a concentration of 2.5% in 85% aqueous ethanol; and into ahandkerchief perfume at a concentration of 20% (in 95% aqueous ethanol).A distinct and definite strong fragrance as set forth in Table VI belowis imparted to the cologne and to the handkerchief perfume:

    ______________________________________                                        Compound       Aroma                                                          ______________________________________                                        3-methylthio-4-heptanol                                                                      A sweet, green, floral, herbal,                                               vegetative aroma with an                                                      underlying verdima nuance.                                     3-methylthio-4-heptanone                                                                     A green, minty, herbaceous aroma                                              with basil nuances.                                            3-propylthio-4-heptanol                                                                      A green aroma with floral nuances.                             3-thioacetyl-2,6-dimethyl-                                                                   A grapefruit oil-like aroma.                                   4-heptanone.                                                                  3-isobutylthio-4-heptanone                                                                   A green, spicey and peppery                                                   aroma with an underlying bergamot                                             note.                                                          3-isobutylthio-2,6-dimethyl-                                                                 A green aroma containing notes                                 4-heptanol     of hyacinth and narcisse.                                      3-methylthio-2,6-dimethyl-                                                                   A sweet, slightly floral and                                   4-heptanone    woody aroma with fruity and                                                   berry nuances.                                                 3-(methyallythio)-2,6-                                                                       A fruity, grapefruit, somewhat                                 dimethyl-4-heptanone                                                                         floral aroma with underlying                                                  yara and neroli notes and                                                     bready, vegetative nuances.                                    ______________________________________                                    

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a NMR spectrum for the product of Example I(B) wherein3-thioacetyl-4-heptanone is produced.

FIG. 2. is the infrared spectrum for the product of Example I(B) wherein3-thioacetyl-4-heptanone is produced.

FIG. 3 is the NMR spectrum for the product of Example I(C) wherein3-thiomethyl-4-heptanone is produced.

FIG. 4 is the infrared spectrum for the product of Example I(C) wherein3-thiomethyl-4-heptanone is produced.

FIG. 5 is the NMR spectrum for the product of Example I(D) wherein3-thiomethyl-4-heptanol is produced.

FIG. 6 is the infrared spectrum for the product of Example I(D) wherein3-thiomethyl-4-heptanol is produced.

FIG. 7 is the NMR spectrum for the product of Example II(C) wherein3-methallylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 8 is the infrared spectrum for the product of Example II(C) wherein3-methallylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 8(A) is the NMR spectrum for the product of Example II(D) wherein3-thioacetyl-2,6-dimethyl-4-heptanone is produced.

FIG. 8(B) is the infrared spectrum for the product of Example II(D)wherein 3-thioacetyl-2,6-dimethyl-4-heptanone is produced.

FIG. 9 is the NMR spectrum for the product of Example III(A) wherein3-propylthio-4-heptanone is produced.

FIG. 10 is the infrared spectrum for the product of Example III(A)wherein 3-propylthio-4-heptanone is produced.

FIG. 11 is the NMR spectrum for the product of Example III(B) wherein3-propylthio-4-heptanol is produced.

FIG. 12 is the infrared spectrum for the product of Example III(B)wherein 3-propylthio-4-heptanol is produced.

FIG. 13 is the NMR spectrum for the product of Example IV wherein3-isobutylthio-4-heptanone is produced.

FIG. 14 is the infrared spectrum for the product of Example IV wherein3-isobutylthio-4-heptanone is produced.

FIG. 14(A) is the NMR spectrum for the product of Example V(A) wherein3-isobutylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 14(B) is the infrared spectrum for the product of Example V(A)wherein 3-isobutylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 15 is the NMR spectrum for the product of Example V(B) wherein3-isobutylthio-2,6-dimethyl-4-heptanol is produced.

FIG. 16 is the infrared spectrum for the product of Example V(B) wherein3-isobutylthio-2,6-dimethyl-4-heptanol is produced.

FIG. 17 is the NMR spectrum for the product of Example VI wherein3-methylthio-2,6-dimethyl-4-heptanone is produced.

FIG. 18 is the infrared spectrum for the product of Example VI wherein3-methylthio-2,6-dimethyl-4-heptanone is produced.

What is claimed is:
 1. A perfumed article comprising at least onecompound having the structure: ##STR72## wherein R is one of hydrogen ormethyl and X is a ketone group having the structure: ##STR73## and Y isselected from the group consisting of methyl, methallyl having thestructure: ##STR74## 1-propyl, 2-methyl-1-propyl and acetyl, and a soapor detergent.
 2. The perfumed article of claim 1 wherein R is hydrogenand Y is methyl.
 3. The perfumed article of claim 1 wherein R is methyland Y is methallyl.
 4. The perfumed article of claim 1 which is adetergent composition.
 5. The perfumed article of claim 1 which is asoap composition.